Condensation product and method of making same.



LEO H. BM I1 1' OF YQNKERB, NEW YORK.

CONDENSATION PRODUCT AND METHOD OF MAKING BAKE.

Specification 0t Letters Patent.

Patented Dec. 7, 1909.

We Drawing. Applicatlon filed fiotober 15, 1807, Serial Ho. 897,660. Renewed September 17, 1909. Serial No. anaaaa.

To all whom it may concern:

Be it known that I, Lao H. Bastian mo, a citizen of the United States, residing at Yonkers, in the county of \Vestchester and State of New York, have invented certain new and useful Improvements in Condensation Products and Method of Making Same, of which the following is a specification.

This invention relates to an improved method of reacting with formaldehyde upon phenol or a phenolic body, and the improved product resulting from such reaction.

The condensation products resultin from the chemical action of aldehydes onp enols have received by further treatment some industrial applications in the manufacture of varnishes, resinous products and plastic compounds. In some cases such condensation products have been pre ared by simple boiling or heating of pheno and formaldehydc without the addition of condcnsin agents; but such treatment does notm al cases yield the desired result, and at best the motion is very slow, reauirmg about eight hours boiling with or ina commercial phenol and formaldehyde. ith pure crystallized phenol the reaction does not occur even after forty-eight hours constant boiling. It has also been proposed to use acids or salts as condensing agents, but the employment of these results in a stormy reaction, often diflicult to control, and yields products containing undesirable impurities which it is difiicult or impracticable to eliminate, these im urities havin the effect of causing the resu tin mass to arken with age or in presence of a kalies.

I have discovered that the addition in proper proportions of an or anic or inorganic base to a mixture of p enol and formaldehyde, or to either component of the mixture, facilitates the reaction and yields products which are commercially far superior to those obtained by simple heating or by the use of acids or salts as condensing agents. The proportion of henol to for maldeh de may be considerably varied, the formal ehyde being present in about the molecular proportion required for the reaction or in excess thereof. The base may be added at any phase of the process either at the start or during the heating of the mixture, or in successive portions as the heating prs.

According to my invention the alkalies or bases are used in such relatively small proortions that their presence does not interere with the desirable qualities of the products, rendering it unnecessary to eliminate them by washing or neutralizing. In fact in most cases the small amount 0 base persists in the final products and confers upon them new and desirable properties.

By reason of their comparative cheapness it is preferred to em loy as a condensing agent ammonia, anhy rous or'aqueous, ammonium carbonate, caustic alkahes or their carbonates, anilin or yridin, but other bases as for instance the hydrates of barium, strontium, or calcium may be used. Amins and amids, and in encral all derivatives of the t pe N H, whic possess basic properties are ound to act in the same manner. Similarly all basic salts, or salts which by soconda reaction engender bases, as'ior instance a kali sulfids, acetates and cyanids, sodium triphos hate, borax, soaps, etc, may be used; a so alkali sulfites ma serve, for the reason that when boiled with formaldehyde they liberate alkali in accordance with the well known reaction:

cn, on so,na+mon The bases above referred to, and others having the requisite basic properties, are employed in variable roportlons, according to their character and also according to the result desired. Additions of ammonia or caustic soda in so small a roportion as one half per cent. of the weight of phenol used show a decided influence, but in most cases it is desirable to use somewhat larger proportions, rarely attainin however 10% by weight of the henol or p ienolic bod The proportion o bases used as con ensing agents has a pro onderant influence on the nature of the u timate products. For instance, if a large amount of ammonia be used,hexamethylentetramin is formed, which 15 a crystalline body of definite chemical roperties. (See Wohl, Ben, 19, 1892; T01- ens, Ben, 17, 653. See also Moschatos and Tollens Ann. der C'lwmie, 272, 280.) Likewise, if large amounts of'caustic soda be used there are obtained alkaline derivates of henol-alcohol. (See Lederer, Journal P tiache Uhemie (2), Vol. 50, page 224,

- and Manasse U.S.P.526,786,1894). It is therefore essential that the proportion of base should not exceed certain definite limits, and the maximum permissible prortion has been found to be less than onefth of the equimolecular proportion of phenolic bod present. If larger proportions of base be used there are forme in the mass such amounts of disturbing bodies as serve to render the product technical] inferior or worthless for the purposes 0 this invention.

It should be understood that in the case of such basic compounds as alkali sulfids, cyanids, sodium triphosphate, or those that yield bases by reaction as for instance the alkali sulfites, the proportion of salt to be used should be calculated in proportion to the quantity of base liberated.

In car mg the process into etl'ect the reacting b ies are brought to ether in a suitable vessel, the most availab e bodies being ordinary phenol, ure or commercial, (the latter containing the homolo ues of phenol) and formaldehyde. If the amse be strong or the amount of the same relatively large the reaction ma begin at ordinary temperatures, and wil be usually indicated by a separation of the liquid mixture into two superposed layers, viz., an aqueous layer consisting of se arated water containing some water-solube materials, and an oily layer containing the initial products of dehydration. The reaction is rendered more complete by heat, and this may be applied in a closed vessel, or in a vessel provided with a return condenser, in such manner as to avoid any loss of volatile materials.

The progress of the reaction may be followed by noting the increasing viscosity of the oily liquid. The heating is interrupted after a suitable consistence for the purposes in view has been attained, this condition being often reached in the course of a very few minutes. Continuation of the reaction yields a more or less viscous, elastic or semisolid product, which for certain purposes may be preferred to the oily liquid above referred to. The oily liquid is found to be soluble in alcohol, acetone and similar solvents, and in con unction with these forms varnishes of excel ent quality.

Application of heat under roper conditions to the dry varnish ren ers it insoluble in all ordinary solvents, and substantially inert to acid and alkaline reagents. Instead of dismlving the oily liquid directly, it may first be concentrated further; such treatment is found to improve somewhat the qualities of the product for general purposes. It is not necessary to withdraw the oily liquid from the supernatant aqueous li nor, but the whole may be submitted to furt icr cvaporation, even to the int of becomin elastic, semi-solid or even solid at norma ceases temperatures, the mass being still fusible and soluble m alcohol or in a mixture of alcohol and acetone.

The mass produced as above described may be hardened and rendered insoluble by the a plication of heat at temperatures below t e boiling point of water, but it will require heating or a period rangin from several days to several weeks before t e final product is sutiiciently hard. However by submitting the mass under pressure in a closed vessel or mold to a higher temperature, say 120-200 C., or even higher, as described in my co-pending application, Ser. No. 383,684, filed July 13, 1907, a compact mass of excellent properties may be quickly obtained; or a moderate tem eruture may be a plied until the mass has come superficially hardened, and this may be followed by the application of a relatively hi h gree of heat to complete the ham cmng process.

The above treatment yields a mass which is insoluble in alcohol and all ordinary solvents, and which is unuti'ected or but littlc ati'ected by acids, alkalies, and all ordinary chemical reagents. The mass is resistant to heat, withstandin temperatures as high as 300 0., and is ini usible at all temperatures. It difl'ers mainly from the product prepared in accordance with my copcndiu application above referred to in that the asic condensing agent used ersists in the final roduct as well as in t ie intermediate stages eading thereto.

A wide variety of compositions may be prepared by incorporating solid, semi-solid. or liquid materials of the most varied nature, the addition of such substances bein made at an desired stage of the )locess, eit er before the reagents are mixe or to the mass resulting from their reaction, or at any time before or during the final hardening. Any desired color may be imparted to the product by the addition of suitable dyes or pigments.

As examples of desirable proportions of the ingredients the following may be mentioned:

Example 1: Phenol 50 parts by weight, commercial formaldehyde 30 to parts by weight, aqueous ammonia 1 to 10 parts by wei ht.

Example 2: Phenol 50 parts by weight, commercial formaldehyde 30 to 70 parts by wci ht, nniliu 1 to 7 parts by weight.

ltxumplc Sl: lhcuol 50 parts by weight, commercial formaldehyde 30 to 70 parts by weight, commercial sodium or potassium hydroxid or carbonate 0.5 to 6 parts by weight.

I am aware that it has been proposed to dissolve phenol in substantially molcculur proportions of caustic alkali with formation lOt of a phenolate, then to react upon the phenolate with formaldehyde, afterward neutralizin the alkali by means of acid, the prod act in this case being a solid soluble in alcohol and in caustic )otash. (Sec French Patent No. 361,539 to )eLaire.) My method differs from the above in that it does not contemplate the employment of alkali in the large proportion described, rendering necessary its subsequent neutralizat on; and my roduct differs from that described above in that instead of being a solid soluble in alcohol it is a mass, capable of being molded and of forming homo cneous mixtures, and yielding under the in uences of heat or of heat and pressure a solid mass insoluble in alcohol and in all other ordinary solvents and substantially unatl'ected by acid or alkaline reagents.

ll claim:

1. The method which consists in reacting on a phenolic body with formaldehyde in presence of a base serving as a COIN ensmg agent, the proportion of base in the productbeing less than oncfifth of the equimolectr lar proportion of the phenolic body'used.

2. The method which consists in reacting on a phenolic body with formaldehyde in reseuce of a base serving as a condensing agent, the proportion of base in the product. b ing less than one-fifth of the equimolecular proportion of the phenolic body used, and separating water from the resulting product.

3.'The method which consists in reacting on a phenolic body with formaldeh de in resence of a base serving as a con ensing agent, the proportion of base in the product being less than one-fifth ofthe equimolecular proportion of the phenolic body used, separatingI water from the resulting product, and t on hardening the same.

a. The method which consists in reacting on a phenolic body with formaldehyde in presence of a base serving as a condensing agent, the proportion of base in the product b ing less than one-fifth of the equimoleeular proportion of the hcnolic body used, parating water from t e resulting product, and then iardening the same by application of heat and pressure.

5. The method which consists in reacting on a phenolic body with formaldeh de in presence of a base serving as a con ensing agent, the proportion of base in the product being less than one-fifth of the equimolecular proportion of the )henolic body used, compoundin the resulting body with a suitable materia and then hardening the composition.

6. The method which consists in reacting on a phenolic body with formaldehyde in presence of a base serving as a condensing agent, the proportion of base in the product being less than one-fifth of the equimolecular proportion of the henolic body used, compoundin the resulting body with a suitable materia and then hardening the composition by application of heat and )ressure.

7. The herein described con ensation product resultin from the reacting of a phenolic body an formaldehyde in presence of a base serving as a condensing agent, the proportion of base in the product being less than one-fifth of the e uimolecular pro ortion of the phenolic bod used, said pro net varying in its physica characteristics in accordance with the reacting conditions, and characterized by the presence of the free or combined base in quantities not exceeding the above proportions, by its insolubility in water, its solubility in alcohol or acetone, and by its capacity for transformation under heat and ressure into a solid body insoluble in alcoho acetone or like solvents, or in acid or alkaline rea ents.

8. The herein escribed condensation product resultin from the reaction of a phenolic body an formaldehyde in presence of a basic condensing agent, said condensation product characterized by its hardness, its insolubility in waterand all known solvents, by its infusibilit or resistance to heat, and by the presence tierein of a proportion of 'free or combined base not exceeding onefifth of the equimolecular proportion of phenolic body employed.

In testimony whereof, atlix my signature in presence two witnesses.

LEO H. BAEKELANI).

Witnesses:

Faun R. Caner, H S. Taannnn. 

